2,6,7-trioxa-1-arsabicyclo{8 2.2.2{9 octane compounds

ABSTRACT

Novel derivatives of 2,6,7-trioxa-l-arsabicyclo( 2.2.2)octane are useful as pesticides. The compounds are represented by the general formula   WHEREIN Z can be alkyl, aryl, aralkyl, alkaryl, cycloalkyl, alkoxy, aryloxy, acyl, acyloxy, acyloxymethyl, benzoxymethyl, amino, nitro, nitrobenzoxymethyl, ammonium nitrobenzoate and chrysanthemumoxymethyl. Examples include 4-PROPYL-2,6,7-TRIOXA-1-ARSABICYCLO(2.2.2)OCTANE 4-NITRO-2,6,7-TRIOXA-1-ARSABICYCLO(2.2.2)OCTANE 4-AMINO-2,6,7-TRIOXA-1-ARSABICYCLO(2.2.2)OCTANE 4-ACETOXYMETHYL-2,6,7-TRIOXA-1-ARSABICYCLO(2.2.2)OCTANE 4-BENZOXYMETHYL-2,6,7-TRIOXA-1-ARSABICYCLO(2.2.2)OCTANE 4-(P-NITROBENZOXYMETHYL)-2,6,7-TRIOXA-1-ARSABICYCLO(2.2.2)OCTANE 4-CHRYSANTHEMUMOXYMETHYL-2,6,7-TRIOXA-1-ARSABICYCLO(2.2.2)OCTANE 2,6,7-TRIOXA-1-ARSABICYCLO(2.2.2)OCTYL-4-AMMONIUM PNITROBENZOATE.

United States Patent [72] Inventor [2i Appl. No. [22] Filed [45) Patented [73] Assignee 54] 2,6,7-TRIOXA-l-ARSABICYCLOI2.2.21OCTANE COMPOUNDS 9 Claims, No Drawings [52] US. Cl 260/440, 424/297, 424/306, 71/97 [51] int. Cl. C07f 9/78, AOln 9/00, AOln 9/24 [50] Field ol Search 260/440 [56] References Cited UNITED STATES PATENTS 3,351,649 1 H1967 Gradsten 260/440 Primary Examiner-Tobias E. Levow Assistant Examinerwerten F. W. Bellamy Attorneys-Meyer Neishloss, Deane E. Keith and William H.

Deitch ABSTRACT: Novel derivatives of 2,6,7-trioxa-l-arsabicyclo[2.2 .2loctane are useful as pesticides. The compounds wherein Z can be alkyl, aryl, aralkyl, alkaryl, cycloalkyl, a1- koxy, aryloxy, acyl, acyloxy, acyloxymethyl, benzoxymethyl, amino, nitro, nitrobenzoxymethyl, ammonium nitrobenzoate and chrysanthemumoxymethyl. Examples include 4-propyl-2,6,7-trioxal -a|;sabicyclo[ 2.2.2 loctane 4-nitro-2,6,7-trioxal -arsabicyclo[2.2.2 loctane 2,6,7-TRIOXA-l-ARSABICYCLO[2.2.2]OCTANE COMPOUNDS This invention relates to certain novel derivatives of 2,6,7- trioxa-l-arsabicyclo[2.2.2]octane which are useful as pesticides including insecticides and herbicides.

The derivatives of 2,6,7-trioxa-l-arsabicyclo[2.2.2.]octane of this invention are represented by the following general formula wherein Z is selected from the group consisting of alkyl[C,,,H sun-ii y i s s i io 1 ii y l s u Qrl;

m is an integer of 3 to 8; and n is an integer of l to 8. Specific examples of compounds of the invention are 4-propyl-2,6,7-trioxa-l-arsabicyclo[2.2.2]octane 4-nbutyl-2,6,7-trioxa-l-arsabicyclo[2.2.2.]octane 4-tert-butyl-2,6,7-trioxa- 1 -arsabicyclo[ 2.2.210ctane 4-n-amyl-2,6,7-trioxal -arsabicyclo[2.2.2 ]octane 4-isoamyl-2,6,7-trioxa-l-arsabicyclo[2.2.2. ]octane 4-n-hexyl-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-isohexyl-2,6,7-trioxa-l-arsabicyclo[2.2.2 ]octane 4-n-heptyl-2,6,7-trioxal -arsabicyclo[2.2.2]octane 4-n-octyl-2,6,7trioxal -arsabicyclo[ 2.2.2]octane 4-isooctyl-2,6,7-trioxal -arsabicyclo[2.2.2]octane 4-phenyl-2,6,7trioxa-l-arsabicyclo[ 2.2.2loctane 4-naphthyl-2,6,7-trioxa-l-arsabicyclo[2.2.21octane 4-benzyl-2,6,7-trioxal -arsabicyclo[2.2.2. ]octane 4-phenethyl-2,6,7-trioxal -arsabicyclo[2.2.2]octane 4-tolyl-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-xylyl-2,6,7-trioxal -arsabicyclo[2.2.2]octane 4-cyclohexyl-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-methoxy-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-isooctyloxy-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-phenoxy-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-naphthoxy-2,6,7-trioxal -arsabicyclo[ 2.2.21octane 4-acetyl-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-butyryl-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-isooctanoyl-2,6,7-trioxal -arsabicyclo[2.2.2]octane 4-acetoxy-2,6,7-trioxa-l-arsabicyclo[2.2.2]octane 4-propionyloxy-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-butyryloxy-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-isooctanoyloxy-2,6,7-trioxal-arsabicyclol 2.2.2 ]octane 4-acetoxymethyl-2,6,7-trioxa- 1 -arsabicyclo[2.2.2]octane 4-propionyloxymethyl-2,6.7-trioxal arsabicyclo[2.2.2]octane 4-butyryloxymethyl-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-valeryloxymethyl-2,6.7-trioxal -arsabicyclo[ 2.2.21octanc 4-caproyloxymethyl-2 .6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-isohcptunoyloxymcthyl-2 ,6,7-trioxal -arsabicyclo[ 2.2.2

]octane 4-isnoctunoyloxymethyl-2.6,7-trioxal -arsabicyclo[ 2.2.2

luclune 4apelnrgrmyloxymethyl-2.6.7-triuxul -ursubicyclol 2.2.2

|octunc 4-isodecanoyloxymethyl-2,6,7-trioxal -arsabicyclo[ 2.2. 2

]octane 4-benzoxymethyl-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-amino-2,6,7-trioxa-l-arsabicyclo[2.2.2octane 4-nitro-2,6.7-trioxal -arsabicyclo[ 2.2.21octane 4-p-nitrobenzoxymethyl-2,6,7-trioxal -arsabicyclo[ 2.2.2.

]octane 2 ,6,7-trioxal -arsabicyclo[ 2.2.2 loetyl-4 ammonium nitrobenzoate 4-chrysanthemumoxymethyl-2,6,7-trioxal -arsabicyclo[2.2.2]octane The novel derivatives of 2,6,7-trioxa-l-arsabicyclol 2.2.21octane of this invention are in general, liquid or solid compounds, the solids melting at low or moderate temperatures. They are stable at nonnal atmospheric conditions of temperature and pressure and can be readily prepared and stored without special precautions for future use. The compounds of the invention are found to have insecticidal and herbicidal activity.

The compounds of the invention can be variously prepared. The C to Q, alkyl derivatives of 2,6,7-trioxa-l-arsabicyclo[ 2.2.2loctane, for example, can be prepared by reacting arsenic trioxide wit the appropriate l,l,,l-tris(hydroxymethyl)alkane. Examples of suitable l,l,l-tris(hydroxymethyl )alkanes are l l l-tris( hydroxymethyl)butane l, l l-tris(hydroxymethyl)pentane l ,l l -tris( hydroxymethyhhexane l l l -tris( hydroxymethyl )heptane l, l l -tris( hydroxymethyl )octane l, l l-tris( hydroxymethyl )nonane The reaction between the l,l,l-tris(hydroxymethyl)alkane and arsenic trioxide is illustrated by the equation where R is an alkyl group containing from three to eight carbon atoms. The reaction between the arsenic trioxide and the l,l,l-tris(hydroxymethyl)alkane is preferably conducted in the presence of an inert organic solvent under refluxing conditions. Suitable solvents include benzene, toluene, xylene, chlorofon'n and carbon tetrachloride. Refluxing is continued until the theoretical amount of water is released. The reaction mixture is filtered to remove undesired starting materials. Solvent is then stripped from the filtrate under reduced pressure to produce a residue containing the alkyl derivative of 2,6,7- trioxa-l-arsabicyclo[2.2.2]octane. The desired alkyl derivative can be recovered and purified according to known techniques including solvent extraction, filtration, recrystallization, sublimation, or the like, dependent upon the nature of the particular compound.

The amino and nitro derivatives of 2,6,7-trioxa-l-arsabicyclo[2.2.2]octane can be prepared by reacting tris(hydroxymethyl)aminomethane and tris(hydroxymethyl)nitromethane respectively, with arsenic trioxide in the presence of an organic solvent under conditions similar to those used in preparing the C to C alkyl derivatives of 2,6,7- trioxal -arsabicyclo[2.2.2]octane.

The p-nitrobenzoic acid salt of 4-amino-2,6,7-trioxa-l-arsabicyclo[2.2.2octane can be prepared by a conventional acid-base reaction between p-nitrobenzoic acid and 4-amino- 2,6,7-trioxa-l-arsabicyclo[2.2.2]octane.

The acyloxymethyl derivatives of 2,6,7-trioxa-l-arsabicyclo[2.2.2]octane can be prepared by reacting 4-hydrox-. ymethyl-2,6,7-trioxa-l-arsabicycl0[2.2.2]octane with the appropriate acid anhydride. Examples of suitable acid anhydrides which can be used are acetic anhydride, propionic anhydride, n-butyric anhydride, n-valeric anhydride, caproic anhydride, enanthic anhydride, caprylic anhydride, pelurgonic anhydride and capric unhydride. The reaction of 4-hydr0xymethyl-2,6.7-trioxa-l-ursabicyclol 2.2.2loctnnc with the acid anhydride is illustrated by the equation (H) CH2- where R is hydrogen or an alkyl group containing from one to eight carbon atoms.

The benzoxymethyl, nitrobenzoxymethyl and chrysanthemumoxymethyl derivatives of 2,6,7-trioxa- 1 -arsabicyclo[2.2.2]octane can be prepared by reacting 4-hydroxymethyl-2,6,7-trioxa-l-arsabicyclo[2.2.2]octane with the appropriate carbonyl halide. Examples of suitable carbonyl halides which can be used are benzoyl chloride, nitrobenzoyl chloride and chrysanthemumoyl chloride. The reaction of 4- hydroxymethy1-2,6,7-trioxa-l-arsabicyclo[2.2.2]octane with the carbonyl halide is illustrated by the equation where A is a benzoyl, nitrobenzoyl or chrysanthemumoyl group. The reaction between the carbonyl halide and the 4- hydroxymethyl-2,6,7-trioxal -arsabicycl0[ 2. 2.2 ]octane is preferably conducted in the presence of an organic solvent such as benzene, toluene, xylene chloroform, ocetone and carbon tetrachloride. The reaction is accelerated by the use of basic material such as pyridine, triethylamine, sodium hydrox ide and the like. The reaction is carried out under reflux conditions which may be at a temperature within the range of about 35 to about 150 C. depending upon the pressure and the particular solvent which is used. The reaction can be conducted at autogenous pressure for a period of about A to 24 hours or more. Upon completion of the reaction the product is recovered by removal of the solvent as by vacuum distillation. If desired, purification of the product is efiected by repeated recrystallizations from a solvent such as acetone or benzene.

The aryl, aralkyl, alkaryl, cycloalkyl, alkoxy, aryloxy, acyl and acyloxy derivatives of 2,6,7-tn'oxa-1-arsabicyclo{ 2.2.2]octane can be prepared by procedures similar to those described hereinabove.

The following examples illustrate specific procedures by which compounds of the invention can be prepared.

EXAMPLE 1 4-Propyl-2 ,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane A mixture of 19.8 grams (0.1 mole) of arsenic trioxide and 29.6 grams (0.2 mole) of 1,1,1-tris(hydroxymethyl)butane dispersed in 120 milliliters of toluene is stirred and refluxed at about 1 C. in a flask connected to a reflux condenser by means of a Dean-Stark trap. Refluxing is continued until the theoretical amount of water (5.4 grams) is collected in the trap. The resulting solution is filtered and concentrated under vacuum to remove the solvent. The crude product (43 grams) is purified by sublimation at 60 C. and 0.1 mm. of mercury pressure. The purified product (35.8 grams) has a melting point of 48.549.5 C. The yield is about 8 l .5 percent of the the theoretical yield. Elemental analysis of the product shows it to compare favorably with the theoretical analysis of 4- propyl-2,6,7-trioxa-1arsabicyclo[2.2.2]octane.

Percent by weight for 4-Propyl- 2,6,7-trioxal-arsabicyclo[ 2.2.2]octane Found Theoretical Carbon 38.25 38.20

Hydrogen 5.65 5.95

EXAMPLE ll 4-Nitro2,6,7-trioxa-1-arsabicyc1o[2.2.2]octane Arsenic trioxide (19.8 grams; 0.1 mole), l,1,1-tris(hydroxymethyl)nitromethane )(30.2 grams; 0.2 mole) and a catalytic amount (0.25 gram) of toluene sulfonic acid are refluxed in toluene as in example I. The product, after purification, has a melting point of 187 C. Elemental analysis of the product shows it to compare favorably with the theoretical analysis of 4-nitro-2,6,7-trioxa-1-arsabicyclo[2.2.2]octane.

4-Amino-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane Arsenic trioxide (19.8 grams; 0.1 mole) and 1,1,1- tris( hydroxymethyl)aminoethane (24.2 grams; 0.2 mole) are refluxed in toluene as in example 1. The product, after purification, has a melting point of 87 C. The yield is 75 percent of the theoretical yield. Elemental analysis of the product shows it to compare favorably with the theoretical analysis of 4- amino-2,6,7-trioxa- 1 -arsabicyclo[ 2.2.2 ]octane Percent by weight for 4-Amino-2,6,7-trioxa-l-arsabicyclo[ 2.2.2 ]octane Found Theoretical Carbon 24.72 24.99

Hydrogen 4.13 4.18

Nitrogen 7.47 7.26

EXAMPLE 1V 2 ,6,7-Trioxal -arsabicyclo[ 2.2.2 ]octyl-4-ammonium-pnitrobenzoate 4-Amino-2,6,7-trioxa-1-arsabicyclo[2.2.2]octane 19.3

grams; 0.1 mole) obtained as described in example 111 and pnitrobenzoic acid (16.7 grams; 0.1 mole) are refluxed in tetrahydrofuran. The melting point of the 2,6,7-trioxa-l-arsabicyclo[2.2.2]octyl-ammonium-p-nitrobenzoate thus obtained is 105 C.

EXAMPLE V 4-Acetoxymethyl-2,6,7-trioxa-1-arsabicyclo[2.2.2]octane A mixture of 19.8 grams (0.1 mole) of arsenic trioxide and 27.2 grams (0.2 mole) of pentaerythritol dispersed in milliliters of toluene is stirred and refluxed at about 1 10 C. as in example 1 until the theoretical amount of water (5.4 grams) is removed from the reaction mass. The product after purification has a melting point of lO2-l04.5 C. and comprises 4- point of 87-90 C. The yield is about 53.6 percent of the:

theoretical yield. Elemental analysis of the product shows it to compare favorably with the theoretical analysis of 4-acetoxymethyl-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane.

Percent by weight for 4-Acetoxymethyl-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane Found Theoretical Carbon 33.93 33.62

Hydrogen 4.32 4.43

EXAMPLE Vl 4-Benzoxymethyl-2,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane 4-Hydroxymethyl-2,6,7-trioxa-1-arsabicyclo[2.2.2]octane 10.4 grams; 0.05 mole) obtained as described in example V is mixed with 200 milliliters of dry benzene and 4.0 grams (0.05 mole) of pyridine. The mixture is stirred and a solution of benzoyl chloride (7.2 grams; 0.05 mole) in 50 milliliters of benzene is added over a l-hour period. The mixture is refluxed for 2 hours. The reaction mass is cooled and filtered. The filtrate is evaporated under a reduced pressure to remove the solvent whereupon 14.7 grams of a white crystalline solid having a melting point of 132 C. is obtained. The yield of crude product is 94 percent of the theoretical yield. Elemental analysis of the product shows it to compare favorably with the theoretical analysis of 4-benzoxymethyl 2,6,7-trioxal-arsabicyclo[2.2.2]octane.

Percent by weight for 4-Benzoxymethyl-2,6,7 -trioxal -arsabicyclo[2.2.2]octane Found Carbon 45.32 46.18 Hydrogen 4.13 4.20

EXAMPLE Vll icyclol 2.2.2 ]octane.

Theoretical Percent by weight for 4( p-Nitrobenzoxymethyl )-2 ,6,7-trioxal -arsabicyclo[ 2.2.2 ]octane Found Theoretical Carbon 41.4 40.4 Hydrogen 3.84 3.39 Nitrogen 4.36 3.92

EXAMPLE Vlll 4-Chrysanthemumoxymethyl-2,6,7-trioxal -arsabicyclo[ 2 2 2 ]octane 4-Hydroxymethyl-2,6,7-trioxa- [-arsabicyclo[ 2.2.2]octane l0.4 grams; 0.05 mole) obtained as described in example V is mixed with 200 milliliters of dry benzene and 4.0 grams (0.05 mole) of pyridine. The mixture is stirred and a solution of chrysanthemumoylchloride (9.3 grams; 0.05 mole) in 50 milliliters of benzene is added over a l-hour period and thereafter refluxed as in example V1. The crude product obtained in this reaction is a yellow liquid. The product is considered to consist essentially of 4-chrysanthemumoxymethyl-2,6,7-trioxa-1- arsabicyclo[2.2.2d]octane.

As has previously been stated, the 2,6,7-trioxa-l-arsabicyclo[2.2.2]octane compounds of the invention constitute a new series of pesticides. Such compounds are found to have insecticidal, herbicidal and plant growth regulant activity. While, obviously, not every compound will have each of these activities, each compound will possess at least one and generally more than one, such activity, The nitrogen containing derivative are particularly useful as herbicides whereas the nonnitrogen containing derivatives are useful as insecticides.

Although the 2,6,7-trioxa1-arsabicyclo[2.2.2]octane compounds of this invention have insecticidal properties of their own, the compounds can be used in conjunction with other insecticide toxicants including pyrethrins and the like. They may be applied to insects in the form of a spray, a granular solid,

dust or powder. The compounds may be dispersed in a suitable extending agent. The compounds may be held in true solution in a suitable solvent or they may be distributed throughout a liquid phase in the form of suspension or emulsions or in the form of particles held in suspension by wetting agents.

The exact concentration of the 2,6,7-trioxa-l-arsabicyclo[ 2.2.2]octane compounds of the invention employed in combatting or controlling insect pests can vary considerably provided the required dosage (i.e toxic or lethal amount) thereof is supplied to the pests or to the environment of the pests. When the extending agent is a liquid or mixture of liquids (e.g., as in solutions, suspensions, emulsions or aerosols) the concentration of the 2,6,7-trioxa-l-arsabicyclo[2.2.2]octane compound employed to supply the desired dosage generally will be in the range of 0.001 to 50 percent by weight. When the extending agent is a solid, the concentration of the 2,6,7- trioxa-l-arsabicyclo[2.2.2]octane compound to supply the desired dosage generally will be in the range of 0.1 to 25 percent by weight. More particularly, the compounds are generally used in amounts of about 50 to about 5,000 milligrams per milliliters of liquid. In a preferred embodiment, 4-propyl-2,6.7trioxal -arsabicyclo[ 2.2.2 ]octane gives excellent insecticidal activity at concentrations in the order of 250 to 1000 milligrams per 100 milliliters of liquid. When used in conjunction with pyrethrins, the compounds may be used in amounts in the order of about 20 to about 2,000 milligrams per 100 milliliters of liquid. The most useful proportions of pyrethrins are between about 20 and about 2,000 milligrams per 100 milliliters of liquid.

The 2,6,7-trioxa-l-arsabicyclo[2.2.2]octane compounds of this invention possess herbicidal activity of a high level. so that an inert carrier is required to obtain uniform distribution on the plants. The compounds may be applied in the form of a spray or a granular solid. When utilized in the form of a spray, the compounds may be dispersed in water along with such auxiliary agents as solvents and surface active agents such as emulsifiers, dispersants or penetrants. When used as a solid, the compounds of the invention may be used in conjunction with kaolin to prevent caking and may be compounded with clays, powdered chalk and other suitable solids as inert carriers and pelletized, if desired, to yield granular solid formations. In preparing formulations of this type it is preferred to use a solvent so as to obtain thorough, even distribution on the inert solid. Other suitable carriers include finely divided tales and synthetic mineral fillers derived from silica and silicates,

for example, synthetic fine silica and synthetic calcium and magnesium silicates. Also magnesium and calcium carbonates can be used.

The amount of active ingredient applied to the area to be protected is sufficient to exert the desired herbicidal action. Different amounts of the active ingredient are suitably applied to achieve a desired result depending upon the extend and nature of weed growth, application procedures and other features. Effective herbicidal action can be obtained by applying the active compound at a rate of about 1 to about pounds per acre, preferably about 5 pounds per acre in most applications. The formulations utilized may contain from 0.5 percent to about 90 percent by weight of active ingredient, depending upon the particular results desired, the method and place of application.

The organic liquids which can be used in preparing solutions, suspensions or emulsions of the 2,6,7-trioxa-l-arsabicyclo[2.2.2]octane compounds of the invention include light petroleum fractions such as deodorized naphthas and kerosenes; lubricating oils of light viscosity; aromatic hydrocarbons such as benzene, toluene, xylene and alkyl naphthalenes such as a-methyl naphthalene; alcohols such as ethanol, propanol and butanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as isopropyl ether; and halogenated compounds such as carbon tetrachloride, ethylene dichloride and tetrachloroethane. In certain instances, it is advantageous to employ a mixture of organic liquids as the extending agent.

When the 2,6,7-trioxa-l-arsabicyclo[2.2.2]octane compound of the invention is supplied as an aerosol, it is convenient to dissolve it in a suitable solvent and disperse the resulting solution in dichlorodifluoromethane or similar 1 chlorofluoroalkane which boils below room temperature at at mospheric pressure.

The insecticidal activity of compounds of the invention is demonstrated by a Primary Immersion Screening Test. When compound is further evaluated by a Microdrop Test Method.

Primary Immersion Screening Test In accordance with this test, about 40 refrigerated flies are spooned into paper lid cages covered with screen When the LII flies recover from refrigeration, they are anesthetized with carbon dioxide and placed on a filter paper in a Buchner funnel. The test compound I mg. in solution or suspension in %v"/u ml. of acetone and 7.5 of water [percent wt./vol. 0.51/1, is poured on the flies and lightly stirred. In a few seconds air is sucked through the funnel to partially dry the flies. The flies are returned to the test cage. At the end of minutes when the flies recover from the carbon dioxide anesthesia, a determination is made of the number of flies that are immobilized. The result is reported as percent knockdown". At the end of 24 hours, a determination is again made of the number of flies that are immobilized. The result is reported as percent dead".

Microdrop Test Method In accordance with the microdrop procedure, the flies (or roaches) which are to be used in the test are first immobilized by placing them for 30 to minutes in a refrigerator at 28 F. The flies are then counted into groups of 25 (roaches are counted into groups of 10) without regard to sex. The 25 flies and/or 10 roaches are then separately placed in disposable cylindrical cages comprising waxed cardboard containers with a wire screen top. The cardboard containers are about A inch in depth and 3% inches in diameter. Four or five cages each of which contains 25 flies (or 10 roaches) are placed in a vessel into which is introduced a constant stream of carbon dioxide. After being exposed to carbon dioxide for about 8 to 10 minutes, the flies and/or roaches are again immobilized. The flies and/or roaches in an immobilized state are removed from the cages and each fly or roach is separately contacted with an acetone or dimethylformamide solution of the test compound. The solution of the test compound is placed in a /c-cc. tuberculin syringe which is inserted in a microdrop applicator. The microdrop applicator is equipped with a hypodermic needle capable of delivering droplets consisting of one microliter of solution. The droplet is placed on the thorax or abdomen of the anesthetized fly and/or roach. Afler all the flies and/or roaches in one container have been treated, the screen lid is replaced on the container which is then placed in a storage rack at 82 F. At the same time, control evaluations are made with untreated flies and/or roaches and with flies and/or roaches treated only with the solvent. Insecticidal activity of the test compound is expressed as percent knockdown after 30 minutes and percent kill after 24 hours with flies, or 48 hours with roaches. During the 24- or 48-hour period, the flies and/or roaches are fed by means of a wad of cotton soaked in 3 50 a 5 percent sugar solution which has been squeezed partially the compound being evaluated shows a marked knockdown in 1 30 minutes or at least 50 percent dead flies in 24 hours, the

dry; the wad of cotton is placed on the screen lid of the container. After the 24- or 48-hour period, the flies and/or roaches are examined and the percent of dead flies and/or roaches is recorded.

The insecticidal activities of compounds of the invention evaluated by the above-described test are summarized in table I.

TABLE I.-INSECTICIDE SCREENING TESTS Microdrop test Immersion test, files Flies Roaches Percent Percent Percent knock Percent knock Percent knock Percent Percent down, dead, down, (lead, down, dead, Compound l wt;./vol. 30 min. 24 hrs 30 min. 24 hrs 30 min. 48 hrs.

1. 0 100 100 0 100 I I t r 0.5 100 100 100 0 70 0. 25 i H2 40 0 10 IL. 0. 50 3 5 U. III. 0. 50 Ill 28 IV l). 50 3 ll] 1.0 IN ll '2!) V 0. 5 100 100 44 88 0 ll] 24 32 0 10 a A 0. l t I O 0 0 l0 TABDE T.INSEC'IICIDE SCREENING TESTS Microdrop test Immersion test, flies Flies Roaches Percent Percent Percent knock Percent knock Percent knock Percent Percent down, dead, down, dead, down, dead, Compound 1 wt./vol. 30 min. 24 hrs. 30 min. 24 hrs. 30 min. 48 hrs.

VI 1.0 0.5 VII 0. VIII 0.5 i

1 Numbers are to the compound of the working example illustrating the preparation of the IV-2,6,7-trioxa-l-arsabicyclol2.2.2]octyl-4-ammonium p-nitrobenzoate.

V-4'acetoxymethyl-2,6,7-trioxa-l-arsabicyclo[2.2.2loctane. VI4-benzoxymethyl-2,6,7-trioxa-1'arsabieycio[2.2.21octane.

VII4-(p-nitrobenzoxyrnethyl)-2,6,7-trioxa-1-arsabicyclo[2.2.2]octane. VIII4-chrysanthemumoxymethy1-2,6,7-trioxa 1-arsabicyclo[2.2.2]octane.

weight of compound in grams 100ml. of solvent Percent wt./vol.=

As evidenced by the data in table I, the nonnitrogen-containing derivatives of 2,6,7-trioxa-l-arsabicyclo[2.2.2]octane are more effective insecticides than the nitrogen-containing compounds. All of the compounds, however, are effective as postemergent herbicides. in order to illustrate the postemergent herbicidal activity of compounds of the invention, aque' ous dispersions of the compound are applied to various crops. The dispersions comprise water as the principle inert carrier, along with such auxiliary agents as solvents and surface active agents such as emulsifiers, dispersants or penetrants. The following formulation is representative of the water-dispersible type suitable for spray application: percent active ingredient, percent solvent (approximately percent xylene and 50 percent kerosene), and percent emulsifier (for example Emulphor 151-719, a polyoxyethylated vegetable oil). About 4 to 5 parts of this emulsifiable concentrate are mixed with about 35 parts of water to produce an aqueous dispersion for spray application.

Aqueous dispersions of compounds of the invention prepared as described above were tested on plants from 10 to 18 days after emergence at application rates of 1,2 and 5 pounds of active ingredient per acre and a spray volume of gallons per acre Seven days after treatment the plants were observed. The results are shown in table ii. The results are rated as follows:

N=necrosis G=growth inhibition O=no effect l=slight efiect (0 to 25 percent foliage) 2=moderate effect (26 to percent of foliage) 3=severe effect (76 to 99 percent of foliage) ft'eme mum f ett sad Plan s) From the results shown in table ll it can be seen that the compounds of the invention are useful for postemergence treatment of certain crops. For example, 4-propyl-2,6,7-trioxa-l-arsabicyclo[2.2.2]octane has only a slight effect on oats, wheat and grain sorghum and yet eliminates soybeans, cotton, alfalfa, sugar beets and tomatoes. It will be noted that 2,6,7- trioxal -a.rsabicyclo[2.2.2 loctyl-4-ammonium-pnitrobenzoate at the rate of 1 pound has no effect on oats and wheat. 4-Benzoxymethyl-2,6,7-trioxal-arsabicyclo[2.2.2]octane at the land 2- pound rate has no effect on oats. 4-(p- TABLE 2.-POST-EMERGENCE HERBICIDE TESTS Rate, Sugar Grain Compound 1 lb./a. Millet Soybean Cotton Alfalfa Oats Corn Flax Radish Beet Wheat sorghum Tomato 5 N2,G2 N4 N4 N4 N1,G2 N2,G2 N3,G3 N3,G3 N4 N1 N1 N4 I 2 N1, G1 N4 N4 N2, G2 N1 N2, G2 N2, G2 N2, G2 N4 N1 N1, G1 N3, G3 1 N1 N4 N2, G2 N2, G2 N1 N2, G2 N2, G2 N1, G1 N4 N1 N1, GI N3, G2

5 N4 N4 N4 N4 N2, G1 N1, G1 N4 N2, G2 N4 N1, G1 N1, G1 N3, G3 II 2 N3, G3 N4 N3, G3 N3, G3 N1 N1, G1 N1, G1 N2, G1 N2, G2 N1, G1 N1, G1 N2, G2 1 N2, G1 N3, G3 N2, G2 N2, G2 N1 N1 1 N1, G1 N2, G2 N1 N1 N2, G1

5 N4 N4 N4 N4 N2, G1 N2, G2 N4 N3, G3 N4 N1, G1 N2, G2 N4 III 2 N3, G3 N4 N4 N4 N1, G1 N1, G1 N2, G2 N2, G2 N4 N1, G1 N2, G2 N4 1 N2, G2 N3, G3 N3, G3 N3, G3 N1 N1, G1 N2, G2 N2, G1 N3, G3 N1 N1, G1 N4 5 N3, G3 N4 N4 N4 N1, G1 N1 N3, G3 N2, G2 N4 N1 N1, G1 N4 IV 2 N3, G3 N3, G3 N4 N3, G3 N1 N1, G1 N2, G1 N2, G2 N4 N1 N1, G1 N3, G3 1 N2, G1 N3, G3 N2, G2 N2, G2 0 N1 N1 N1, G1 N1, G1 0 N1 N2, 02

5 N2, G1 N2, G2 N3, G2 N4 N3, G2 N2, G2 N3, G2 N1, GI N4 N4 N1, G1 N3, G3 V 2 N2, G1 N2, G2 N2, G2 N2, G2 N2, G2 N3, G3 N1, G1 N2, G2 N3, G3 N1 G1 N1 N2 1 N1 N1,G1 N1, G1 N1 N1 N2, G2 N1 N1 N2,G1 N1 0 N1 6 N3, G3 N4 N3, G3 N3, G3 N1, G1 N1 N3, G3 N2, G1 N4 N1, G1 N1, G1 N3, G3 VI 2 N3, G2 N3, G2 N4 N3, G3 0 N1, G1 N3, G3 N1, G1 N3, G3 N1, G1 N2, G1 N2, G2 1 N1, G1 N2 N2, G2 N2, G2 0 N1 N2, G1 N1 N2, G2 N1 N1, G1 N2, G1

6 N2, G2 N3, G3 N2, G2 N4 N3, G3 N1, G1 N4 N2, G2 N4 N3, G3 N1, G1 N3, G3 V I 2 N2, G1 N3, G2 N2, G2 N4 N1 N2, G2 N3, G3 N1 N4 N3, G3 N1, G1 N3, G3 1 N1, G1 N3, G1 N2, G2 N2, G2 N1 N1, G1 N2, G2 0 N3, G3 N2, G2 N1, G1 N2, G2

III I. 5 N1 N2, G1 N1 N3, G3 N1 N1 N2, G2 N1 N1, G1 N2, G2 N1, G1 N3, G3

1 Numbers are to the compound of the working example illustrating the preparation of the compound, The compounds are as follows:

4-propy1-2,6,7-trioxa-1-arsabicyclo[2.2.2]octane II 4-nitro-2,6,7-trioxa-l-arsabicyclo[2.2.2]octane III 4-amino-2,6,7-trioxa-1-arsabicyclo[2.2.2]oetane IV 2,6,7-trioxa-1-arsabicyclo[2.2.2]octyl-4-amm onium p-nitrobenzoate V 4-acetoxymethyl-2,6,7-trioxa-1-arsebicyclo[2.2.2]octane VI 4-benzoxymethyl-2,6,7-tri0Xa-1-arsabicyclo[2.2.2]octane V 4-(p-nitrobenzoxymethyl)2,6,7-trioxa-I-arsabicyclo[2.2.2]octane plants.

II VIII 4-chrysanthemumoxymethyl-2,6,7-trioxa-1arsrbicyclo[2.2.2]octane. No'rE: Ratings: N=Necrosis; G=Growth inhibition; 0=N0 efiect; 1 0 to 25% of foliage; 2=26 to 75% of foliage; 3=76 to 99% of foliage; 4=I l1\(i nitrobenzoxymethyl )-2 ,6,7-trioxal -arsabicyclo[ 2.2.2 loctane at the l-pound rate has no effect on radishes. Various special applications of these compounds. taken alone and in combination will be apparent to those who are skilled in the art.

What is claimed is:

l. A 2,6.7-trioxa-l-arsabicyclo[2.2.2]octane compound represented by the general formula wherein Z is selected from the group consisting of alltyllc l-l acyloxymethyHC x amino nitrobenzosymethyHNO C H COO m is an integer of 3 to 8; and n is an integer of l to 8.

2. 4-Propyl-2,6,7-trioxa-l-arsabicyclo[2.2.2 loctane.

3. 4-Nitro-2,6,7-trioxa-l-arsabicyclo[2.2.2loctane. 4. 4-Arnino- 2,6,7,-trioxa.- l-arsabicyclo[ 2.2.2 loctane.

5. 2,6,7-Trioxa-l-arsabicyclo[2.2.2]octyl-4-ammonium pnitrobenzoate.

icyclo[2.2.2]octane.

9. 4-Chrysanthemumoxymethyl-2,6,7-trioxal -arsabicyclo[2.2.2]octane.

PO-l050 Patent No.

Inventofls) It is certified that error appears in the above-identified patent UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dated November 16, 1971 John F. Deffner and that said Letters Patent are hereby corrected as shown below:

Column 1,

Column 2,

Column 5,

Column Column 7,

Column 8,

Columns 9 line line

line

line

line

line

line

line

line

and 10, Table 2. for Compound I, under the column 18, "alkaryl[CH CB6H should read -alkaryl[CH C I-1 l9, "alkoxy[C HB2n 1O-] should read --alkoxy[C H O-] 7--;

23, "wit" should read with-.

"l75l76.576.5C. should read l75-l76 .5 C..

26 "[2,,2.2d] should read --[2.2 .2]

19, "extend" should read extent.

4, "2/3v7/8 ml. should read l7.5 ml-.

for Oats, "Nl,G2" should read -Nl,Gl--;

for Compound V, under the column for Flax,

"N3,G2" should read --N3,G37

for Compound VI, under the column for Soybean "N3,G2" should read -N2,G2--;

for Compound VII, under the column for Soybean "N3,Gl" should read -N2,Gl-.

continued on page 2 Page 2 22;;83 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N 3,6 Dated November 16, 1971 John F De ffner Inventofls) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 11, line 20, "nitrobenzosymethyl" should read nitrobenzoxymethyl;

line 21, 0 Nc H coo("7E')H should read --[0 Nc H coo H3-.

Sign? :3 f nd sealed LillLl 2317c? (fair of May 1972.

(SE) AL) A I; i103 1,:

TIDW XRD EBFL'FJTCHFFTJP. ROBERT GOTISCHALK AL-Jeuwng Officmr Commissioner of Patents 

2. 4-Propyl-2,6,7-trioxa-1-arsabicyclo( 2.2.2)octane.
 3. 4-Nitro-2,6,7-trioxa-1-arsabicyclo( 2.2.2)octane.
 4. 4-Amino-2,6,7,-trioxa-1-arsabicyclo( 2.2.2)octane.
 5. 2,6,7-Trioxa-1-arsabicyclo( 2.2.2)octyl-4-ammonium p-nitrobenzoate.
 6. 4-Acetoxymethyl-2,6,7-trioxa-1-arsabicyclo( 2.2.2)octane.
 7. 4-Benzoxymethyl-2,6,7-trioxa-1-arsabicyclo( 2.2.2)octane.
 8. 4-(p-Nitrobenzoxymethyl)-2,6,7-trioxa-1-arsabicyclo( 2.2.2)octane.
 9. 4-Chrysanthemumoxymethyl-2,6,7-trioxa-1-arsabicyclo(2.2.2)octane. 